Fate of pharmaceuticals--photodegradation by simulated solar UV-light

The fate of pharmaceuticals in surface waters under solar irradiation was investigated. Photodegradation of pharmaceuticals caused by sun irradiation may be of major significance in the natural elimination process. Based on a data compilation from the literature, the lipid lowering agent metabolite clofibric acid, the iodinated X-ray contrast media iomeprol, which contribute to the adsorbable organic halogen compounds, and the antiepileptic drug carbamazepine were selected. The irradiation experiments were carried out in batch experiments with simulated UV–sunlight. The photodegradation of the pharmaceuticals showed a pseudo-first-order kinetics. The objective of this investigation was to demonstrate that the extent of photoinduced degradation of pharmaceuticals can vary significantly for the different pharmaceuticals and it strongly depends on the water constituents present in solution. The influences of different initial pharmaceutical concentrations, the presence of other pharmaceuticals like carbamazepine or clofibric acid and the presence of natural organic matter on the photochemical degradation rate of pharmaceuticals in aqueous solutions were investigated. Analyses of the pharmaceuticals and their photodegradation products were carried out by high performance liquid chromatography with diode-array and fluorescence detection.     

Influence of the amendment of corn straw on the degradation behaviour of the fungicide dithianon in soil

Degradation studies were conducted with the fungicide (14)C-dithianon under standard conditions for 64 days in soil. The compound is characterized by mineralization losses of approx. 33% and the formation of non-extractable (bound) residues of approx. 63% in 64 days. The microbial activity of the soil was stimulated by an amendment of corn straw simulating post-harvest conditions. This addition of straw decreased the mineralization of the compound initially. At the end of the incubation period, however, the mineralization rate was higher in the straw amended soil compared to the control. The addition of straw increased the amount of radiocarbon in the desorption solutions. Thus higher amounts of incorporated radiocarbon could be found in the biomass of the amended soil. Model calculations show that the straw amendment has a sustained influence on the mineralization of the compound. Potential mechanisms of the effect of dissolved organic matter on the sorption/desorption equilibrium are discussed.     

Characterization of non-extractable residues of the fungicide dithianon in soil using 13C/14C-labelling techniques

The fate of the (14)C-labelled fungicide dithianon in soil is characterized by the formation of non-extractable, "bound" residues of approximately 63% of applied amount in 64 d. Humic acids containing these "bound" residues were isolated after conducting degradation studies of the active ingredient in an orthic luvisol under standardized conditions. In the same way, (13)C-labelled dithianon was incubated in an artificial soil which was produced by humification of (13)C-depleted straw in an incinerated soil. The "bound" residues of the (13)C-labelled dithianon in the humic acid fraction of the artificial soil were analyzed using (13)C-NMR techniques. There was no evidence of a covalent bonding of the residues to the humic substances. Results of polarity gradient high performance thin layer chromatography (AMD-HPTLC) of "bound" residues of the (14)C-labelled dithianon in the humic acid fraction indicate a sequestration process of metabolites into the humic substance as a possible binding mechanism.     

Photodegradation and volatility of pesticides

BACKGROUND AND OBJECTIVES: Among the factors affecting the environmental fate of surface-applied pesticides several biological as well as abiotic factors, such as volatilization and photochemical transformations are of particular interest. Whereas reliable measurement methods and models for estimating direct photodegradation are already available for the compartments of water and atmosphere and individual subprocesses have already been described in detail, there is still a need for further elucidation concerning the key processes of heterogeneous photodegradation of environmental chemicals on surfaces. METHODS: In order to systematically examine the direct and indirect photodegradation of 14C-labeled pesticides on various surfaces and their volatilization behavior, a new laboratory device ('photovolatility chamber') was designed according to US EPA Guideline 161-3. Model experiments under controlled conditions were conducted investigating the impact of different surfaces, i.e. glass, soil dust and radish plants, and environmental factors, i.e. irradiation and atmospheric ozone (O3), on the photodegradation and volatilization of surface-deposited [phenyl-UL-14C]parathion-methyl (PM). RESULTS AND DISCUSSION: Depending on the experimental conditions, parathion-methyl was converted to paraoxon-methyl, 4-nitrophenol, unknown polar products and 14CO2. With respect to the direct photodegradation of PM (experiments without O3), the major products were polar compounds and 14CO2, due to the rapid photochemical mineralization of 4-nitrophenol to 14CO2. Paraoxon-methyl and 4-nitrophenol formation was mainly mediated by the combination of light, O3, and *OH radicals. In radish experiments PM photodegradation was presumably located in the cuticle compartment, which exhibited a sensitized photodegradation, as more unknown products were yielded compared to the glass and soil dust experiments. This could be explained by intensifying the inherent PM degradation in the dark with the same product spectrum. Due to photochemical product formation, which is an antagonistic process to the volatilization of parent compound, the volatilization of unaltered parathion-methyl from each surface generally decreased in the presence of light, particularly in combination with increasing O3 concentrations and *OH radical production rates. CONCLUSION: First results demonstrated that the photovolatility chamber provides a special tool for the systematic evaluation of (a) photodegradation of surface-located pesticide residues, i.e. measuring qualitative aspects of direct and indirect photodegradation together with relative photodegradation rates, and (b) volatilization of pesticides on surfaces by including and optionally varying relevant parameters such as light, atmospheric O3 concentration, surface temperature, air temperature, air flow rate. OUTLOOK: The experimental facility represents an important complement to lysimeter and field studies, in particular for experiments on the volatilization of pesticides using the wind tunnel system. With the photovolatility chamber special experiments on photodegradation, volatilization and plant uptake can be conducted to study key processes in more detail and this will lead to a better understanding of the effects of certain environmental processes on the fate of released agrochemicals contributing to an improved risk assessment.     

Water technology for specific water usage

BACKGROUND: Water is the basis for life and culture. In addition to the availability of water its quality has become a major issue in industrialized areas and in developing countries as well. Water usage has to be seen as part of the hydrological cycle. As a consequence water management has to be sustainable. The aim of the contribution is to give water usage oriented quality criteria and to focus on the technical means to achieve them. MAIN FEATURES: Water is used for many purposes, ranging from drinking and irrigation to a broad variety of technical processes. Most applications need specific hygienic, chemical and/or physical properties. RESULTS: To meet these demands separation and reaction principles are applied. The reuse of water and the application of water treatment with little or no waste and by-product formation is the way to go. Membrane separation and advanced oxidation including catalytic reactions are promising methods that apply natural processes in sustainable technical performance. Thus elimination of specific water constituents (e.g. salts and metals, microorganisms) and waste water cleaning (e.g. pollutants, nutrients and organic water) can be done efficiently. OUTLOOK: Learning from nature and helping nature with appropriate technology is a convincing strategy for sustainable water management.     

Scale Perspectives on Avian Diversity in Western Riparian Ecosystems

Conservation of riparian vegetation in western North America has, in part, emphasized providing habitats for a locally diverse avifauna. Site diversity, especially relative to the number of species present, is generally high within riparian avifaunas. Between-habitat diversity changes across a watershed, with riparian species assemblages differing most from upland assemblages at the highest and lowest elevations. This pattern can be attributed to enhanced avian movements within the riparian vegetation. The corridors for bird movements, in turn, facilitate faunal mixing on a broader scale, influencing regional diversity within landscapes. Riparian ecosystems are viewed as connectors of forests across fragmented landscapes. In western settings, however, they are highly linearized forests transecting watersheds between upland associations of high elevations and very different associations at lower elevations. Regionally, riparian vegetation represents linear islands that are internally both floristically and faunistically dynamic rather than mere bridges of homogeneous vegetation in landscape networks. The significance of riparian vegetation as habitat for western birds has been defined primarily at the local level. Conservation activities favoring site diversity are short-sighted, however, and could have severe consequences for unique elements of riparian avifaunas. Conservation actions must evaluate how local activities alter potential dispersal opportunities for ecological-generalist versus riparian-obligate species. Maintaining the character and integrity of riparian avifaunas requires planning from regional and continental perspectives.     

Differing Modes of Biotic Connectivity within Freshwater Ecosystem Mosaics

We describe a collection of aquatic and wetland habitats in an inland landscape, and their occurrence within a terrestrial matrix, as a “freshwater ecosystem mosaic” (FEM). Aquatic and wetland habitats in any FEM can vary widely, from permanently ponded lakes, to ephemerally ponded wetlands, to groundwater‐fed springs, to flowing rivers and streams. The terrestrial matrix can also vary, including in its influence on flows of energy, materials, and organisms among ecosystems. Biota occurring in a specific region are adapted to the unique opportunities and challenges presented by spatial and temporal patterns of habitat types inherent to each FEM. To persist in any given landscape, most species move to recolonize habitats and maintain mixtures of genetic materials. Species also connect habitats through time if they possess needed morphological, physiological, or behavioral traits to persist in a habitat through periods of unfavorable environmental conditions. By examining key spatial and temporal patterns underlying FEMs, and species‐specific adaptations to these patterns, a better understanding of the structural and functional connectivity of a landscape can be obtained. Fully including aquatic, wetland, and terrestrial habitats in FEMs facilitates adoption of the next generation of individual‐based models that integrate the principles of population, community, and ecosystem ecology.